TWI263579B - Extruded nanocomposite moulded part comprising at least a polycondensate and a nano-filler and a process for its production - Google Patents

Abstract

The invention relates to an extruded moulded part comprising at least a polycondensate with a melt strength such that the polycondensate is not suitable for extrusion applications per se and a nano-filler, and a process for its production. The major advantage of the extruded moulded part and the process according to the invention is that extruded moulded parts containing polycondensate grades with both high and low viscosities are available. It is for example possible to use polyamides and polyesters that have not been after-condensed in the extruded moulded part according to the invention. Preferably, the extruded moulded part according to the invention contains a polyamide with a relative viscosity of less than 4.3 determined in a 1% solution or the polyamide in m-cresol at 25 DEG C. The invention also relates co a process for increasing the melt strength of a polycondensate composition that contains at least a polycondensate by adding an amount of nano-filler to the composition.

Description

經濟部智慧財產局員工消費合作社印製 1263579 A7 p—- ___ B7___ 五、發明說明（彳) 本發明係有關一種包括至少一種聚縮合物的經擠壓模 製部件及其製法。 彼等經擠壓模製部件係普遍知悉者，例如KunststoffMinistry of Economic Affairs Intellectual Property Office Employees Consumption Cooperative Printed 1263579 A7 p-- ___ B7___ V. INSTRUCTION DESCRIPTION (彳) The present invention relates to an extruded molded part comprising at least one polycondensate and a process for the preparation thereof. Their extruded parts are generally known, such as Kunststoff

Handbuch，Becker et al·，Carl Hanser Verlag, Munchen, 1990 〇 於本申請案的文中，”經擠壓模製部件”要了解者爲可以 利用擠壓得到的任何物體，特別者爲膜件，例如扁平膜或 管狀膜，發泡體，薄壁物體，例如瓶子、管件或軟管，厚 壁物體，例如模製型件、管件或板，纖維，單絲或線繩， 例如電纜絕緣體。’膜’要了解者爲其厚度相對於該材料長度 及/或寬度爲小者之材料，其最大厚度爲約2 5 0微米。’ 薄壁物體’據了解者爲一種物體其至少有一部份係由厚度大 於約2 5 0微米且小於約1毫米的材料所構成。’厚壁物體’ 據了解者爲一種物體其至少有一部份係由厚度大於約1毫 米的材料所構成。 ‘擠壓’據了解者爲一種從熔融體形成經模製部件之程序 且其包括至少一將冷卻熔融體形成磨製部件之步驟，例如 熔抽步驟。 先前技藝經擠壓模製部件的缺點在於該聚縮合物具有 一局熔融黏度（Μ V )，特別是高於形成藉助於注射模製 技術所得模製部件的部分之聚縮合物所具Μ V之Μ V。此 點大大地限制所用聚縮合物的選擇。諳於此技者所普遍知 道者，要製造經擠壓模製部件時，製造該模製部件所用的 聚縮合物組成物必須具有良好的熔融加工性◦此係經由選 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝-------訂---------線 (請先閱讀背面之注意事項再填寫本頁) -4- 經濟部智慧財產局員工消費合作社印製 1263579 A7 「 __B7__ 五、發明說明（2 ) 用具有局Μ V的聚縮合物而得者’例如具有經用該聚釀胺 在間一甲酚中的1 %溶液於2 5 °C下測定爲4 . 0或更大 的相對黏度（R V )之聚醯胺◦使用有低Μ V的聚縮合誤 會導致例如破折，例如在膜件的製造中發生者，或甚至於 導致不可能擠壓成膜件和薄壁模製部件。 本發明的目的爲提出一種經擠壓模製部件其包括至少 一種聚縮合物其熔融加工性爲使得該聚縮合物本身不適合 於擠壓應用；及一種得到彼之方法。 本案發名人頃令人訝異地發現一種可經擠壓的模製部 件’其包括至少一種聚縮合物其熔融加工性爲使得該聚縮 合物本身不適合於擠壓應用和一毫微-塡料。令人訝異地 發現此種組成物具有高熔融強度使得該組成物可擠壓成模 製部件。該組成物本身係已知者，例如載於Ε Ρ - A 2 - 6〇5 ，0 〇 5 ( Umtika )之中者，但其不用於擠壓應用 〇 從 EP- A1- 810，260 (BAYER A . G ·)知道一種含有用己內醯胺於細分散氟雲母礦物質存 在中製成的聚醯胺6之膜件。根據 EP - A1 - 810，260，此種膜件具有低氣體穿透 性’而其他性質，例如光澤、透光性和延展性，則相對於 不含細分散氟雲母礦物質的膜件沒有明顯改變。聚醯胺具 有經用該聚醯胺在間一甲酚中的1 %溶液於2 5 °C下測定 爲4 · 3高R V。 本發明經擠壓模製部件的大優點在於至此可以獲得同 本紙張尺度適用中國國家標準（CNS)A4規格（210 297公釐） ------------裝-------^丨訂----------線 (請先閱讀背面之注意事項再填寫本頁) -5- 經濟部智慧財產局員工消費合作社印製 1263579 A7 -—_____B7 五、發明說明（3 ) 時含有高和低兩種黏度的聚縮合物品級之經擠壓模製部件 。例如可以在本發明經擠壓模製部件中使用未經後一縮合 的聚醯胺和聚酯。 本發明經擠壓模製部件的另一項優點在於毫微複合物 料組成物的調配中需要較少的能量，及該組成物的薄可力口 工性較爲佳。如此可導致例如較爲薄的膜件。另一優點爲 一品級的聚縮合物可經由添加或不添加該毫微一塡料而同 時用於擠壓或注射模製。另一優點在於本案發明人發現本 發明模製部件的表面顯示出較大的光澤和透光性，本發明 膜件不會收縮且本發明膜件顯示出較低的氣體穿透率且該 百旲件可以在吹i吴中以遠較爲大的吹滿比例（blow-up ratio )製成。 更槪括g之’本案發明人發現將一量的毫微一塡料添 加到聚縮合物可以導致所得組成物的熔融強度之急遽增加 。本案因而爲有關一種用以增加含有至少一種聚縮合物的 聚縮合物組成物所具熔融強度之方法，其包括添加一量的 毫微-塡料，較佳者添加相對於該聚縮合物爲〇 . 1 -10重量％，更佳者0 · 2 — 7 · 5重量％的該毫微一塡 料。 諳於此技者所知的任何聚合物都可選用爲該聚縮合物 ，特別者聚醯胺、聚酯、聚醚酯、聚碳酸酯、聚酯醯胺及 彼等的摻合物和共聚物。特別者爲選用聚醯胺或聚酯。較 佳者，本發明聚縮合物爲聚醯胺，該聚醯胺具有經用該聚 醯胺在間-甲酚中的1 %溶液於2 5 °C下測定爲小於 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------裝-------訂----------線^^ (請先閱讀背面之注意事項再填寫本頁) -6 - 經濟部智慧財產局員工消費合作社印製 1263579 A7 _________B7______ 五、發明說明（4 ) 4 . 3的相對黏度。 在重複單位之間有酸一醯胺鍵（一 C Ο Ν Η -）的任 何聚合物都可選用爲聚醯胺，更特別者爲從ε -己內醯胺 、6 —胺基己酸、ω -庚內醯胺、7 —胺基庚酸、1 1 一 胺基十一烷酸、9 一胺基壬酸、α 一吡咯烷酮和^ 一哌啶 酮所得聚醯胺與共聚醯胺；於二元胺例如六亞甲基二胺、 十二亞甲基二胺和間二甲苯二胺，與二元羧酸例如對苯二 曱酸、異苯二甲酸、己二酸和癸二酸，的聚縮合中所得之 聚合物和共聚物；上述聚合物和共聚物的摻合物。彼等聚 合物的例子爲耐綸（n y 1 ο η ) 6、耐綸9、耐綸1 1、耐綸 1 2、耐綸4，6和耐綸6，6。較佳者爲選用耐綸6。 原則上，所有常見的聚酯和共聚酯都適合用爲該聚酯 。其例子爲聚苯二甲酸伸烷基酯或其與異苯二甲酸的共聚 物，例如聚苯二甲酸乙二醇酯（Ρ Ε Τ )、聚苯二甲酸丁 二醇酯（Ρ Ε Β )、聚萘二甲酸伸烷基酯，例如聚萘二甲 酸乙二醇酯（Ρ Ε Ν )、聚萘二甲酸丁二醇酯（Ρ Β Ν ) ，聚聯苯二甲酸伸烷基酯，例如聚聯苯二甲酸乙二醇酯及 彼等的共聚物。較佳者爲使用Ρ Ε Τ、Ρ Β Τ、Ρ Ε Ν或 Ρ Β Ν。另外適當者爲嵌段共聚物，其除了上述硬聚酯截 段之外，還含有熱塑性聚酯，從至少一聚醚或脂族聚酯衍 生的軟聚酯截段◦彼等具有彈性體性質的嵌段共聚酯之例 子爲載於例如”Encyclopedia of Polymer Science and Engineering”，Vol.12, pp75 ff. (1988), John Wiley & Son,和 Thermoplastic Elastomers’’，2nd Ex. Chapter 8 (1996), Hauser 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂 --------線 (請先閱讀背面之注意事項再填寫本頁) 1263579 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（5 )Handbuch, Becker et al., Carl Hanser Verlag, Munchen, 1990 In the context of the present application, "extruded molded parts" are understood to be any object that can be obtained by extrusion, in particular a film, for example Flat or tubular films, foams, thin-walled objects such as bottles, tubes or hoses, thick-walled objects such as molded parts, tubes or plates, fibers, monofilaments or cords, such as cable insulation. The 'film' is understood to be a material whose thickness is small relative to the length and/or width of the material, and has a maximum thickness of about 250 μm. A 'thin wall object' is understood to be an object having at least a portion thereof comprised of a material having a thickness greater than about 250 microns and less than about 1 mm. A 'thick-walled object' is understood to be an object consisting at least in part of a material having a thickness greater than about 1 mm. "Extrusion" is understood to be a procedure for forming a molded part from a melt and which includes at least one step of forming a cooled melt into a milled part, such as a stripping step. A disadvantage of the prior art extrusion-molded part is that the polycondensate has a single melt viscosity (Μ V ), in particular higher than that of the polycondensate forming part of the molded part obtained by means of injection molding techniques. After V. This greatly limits the choice of polycondensate used. As is well known to those skilled in the art, when an extruded molded part is to be manufactured, the polycondensate composition used for the molded part must have good melt processability, which is applicable to the Chinese country via the paper size. Standard (CNS) A4 specification (210 X 297 mm) Packing ------- order--------- line (please read the notes on the back and fill out this page) -4- Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1263579 A7 " __B7__ V. OBJECT DESCRIPTION (2) Having a polycondensate having a ΜV", for example, having a 1% solution of the polyamine in m-cresol Polycondensation with a relative viscosity (RV) of 4.0 or greater at 25 ° C using a polycondensation error with a low Μ V causes, for example, a breakage, such as occurs in the manufacture of a membrane member, or It even makes it impossible to extrude the film-forming member and the thin-walled molded part. The object of the present invention is to provide an extruded molded part comprising at least one polycondensate whose melt processability is such that the polycondensate itself is not suitable for extrusion Application; and one way to get one. The name of the case is surprising. It has been found that an extrudable molded part which comprises at least one polycondensate whose melt processability is such that the polycondensate itself is unsuitable for extrusion applications and a nano-dish. It is surprisingly found The composition has a high melt strength such that the composition can be extruded into a molded part. The composition itself is known, for example, in Ε Ρ - A 2 - 6 〇 5 , 0 〇 5 ( Umtika ) , but it is not used for extrusion applications. From EP-A1-810,260 (BAYER A.G.), a film containing polyamine 6 made from the presence of caprolactam in finely dispersed fluoromica minerals is known. According to EP-A1 - 810, 260, such membranes have low gas permeability ' while other properties, such as gloss, light transmission and ductility, are relative to membranes that do not contain finely dispersed fluoromica minerals. There is no significant change. The polyamine has a high RV determined by using a 1% solution of the polyamine in m-cresol at 25 ° C. The great advantage of the extruded molded part of the present invention is that At this point, the Chinese National Standard (CNS) A4 specification (210 297 mm) can be obtained for the same paper scale. ------------Install -------^丨定----------Line (please read the notes on the back and fill in this page) -5- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1263579 A7 -______B7 V. Invention Description (3) Extrusion molded parts of polycondensation grades containing both high and low viscosities. For example, it can be extruded in the present invention. Another use of the later condensed polyamide and polyester is used in the compression molded part. Another advantage of the extruded molded part of the present invention is that less energy is required in the formulation of the nanocomposite composition, and The thinness of the composition is better. This can result in, for example, a relatively thin membrane member. Another advantage is that the first grade polycondensate can be used for extrusion or injection molding at the same time with or without the addition of the nanopatch. Another advantage is that the inventors of the present invention have found that the surface of the molded part of the present invention exhibits a large gloss and light transmittance, the film member of the present invention does not shrink and the film member of the present invention exhibits a low gas permeability and the hundred The piece can be made in a blow-up ratio that is far greater in the blow. Further, the inventors of the present invention have found that the addition of a quantity of nano-twist to a polycondensate can result in a sharp increase in the melt strength of the resulting composition. The present invention is thus directed to a method for increasing the melt strength of a polycondensate composition comprising at least one polycondensate comprising adding an amount of a nano-dye, preferably added relative to the polycondensate. 1. 1 - 10% by weight, more preferably 0 · 2 - 7 · 5 % by weight of the nano-batch. Any polymer known to those skilled in the art may be selected as the polycondensate, especially polyamine, polyester, polyether ester, polycarbonate, polyester decylamine, and blends thereof and copolymerization thereof. Things. In particular, polyamine or polyester is used. Preferably, the polycondensate of the present invention is a polydecylamine having a 1% solution of the polydecylamine in m-cresol at 25 ° C, which is less than the paper scale applicable to the Chinese country. Standard (CNS) A4 specification (210 X 297 mm) ------------Package-------Book----------Line ^^ (Please first Read the notes on the back and fill out this page) -6 - Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1263579 A7 _________B7______ V. Invention description (4) 4.3 Relative viscosity. Any polymer having an acid monoamine bond (a C Ο Ν Η -) between repeating units can be selected from polyamines, more particularly from ε-caprolactam, 6-aminocaproic acid, Polyaniline and copolyamine obtained from ω-heptanoin, 7-aminoheptanoic acid, 1 1 monoaminoundecanoic acid, 9-amino decanoic acid, α-pyrrolidone and oxapiperidone; Diamines such as hexamethylenediamine, dodecamethylenediamine and m-xylenediamine, and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid and sebacic acid, Polymers and copolymers obtained in the polycondensation; blends of the above polymers and copolymers. Examples of such polymers are nylon (n y 1 ο η ) 6, nylon 9, nylon 1, 1 , nylon 2, nylon 4, 6 and nylon 6,6. Preferably, nylon 6 is selected. In principle, all common polyesters and copolyesters are suitable for use as the polyester. Examples thereof are polyalkylene terephthalates or copolymers thereof with isophthalic acid, such as polyethylene terephthalate (polyphthalate), polybutylene terephthalate (Ρ Ε Β ) , polyalkylene naphthalate, such as polyethylene naphthalate (Ρ Ε ), polybutylene naphthalate (Ρ Β Ν ), polyalkylene terephthalate, for example Polyethylene terephthalate and copolymers thereof. Preferably, Ρ Τ Ρ, Ρ Τ Τ, Ρ Ε Ν or Ρ Β Ν is used. Further suitable are block copolymers which, in addition to the above-mentioned hard polyester segments, also contain thermoplastic polyesters, and soft polyester segments derived from at least one polyether or aliphatic polyester have elastomeric properties. Examples of block copolyesters are described, for example, in "Encyclopedia of Polymer Science and Engineering", Vol. 12, pp 75 ff. (1988), John Wiley & Son, and Thermoplastic Elastomers'', 2nd Ex. Chapter 8 ( 1996), Hauser This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------------------- --Line (please read the notes on the back and fill out this page) 1263579 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 5, Invention Description (5)

Ver lag，及其中所提及的參考資料。 有關毫微-塡料，可以使用諳於此技者所知的任何材 料。特別者，’毫微-塡料’據所知係爲由具有高縱橫比的各 向異性粒子所組成的固體物質，例如層狀或纖維狀無機材 料。 例子的縱橫比於本發明中要了解者爲個別粒子的最大 尺寸與最小尺寸之比例。更特定言之，一板的縱橫比爲該 板的長度對其平均厚度的比例，而一纖維的縱橫比爲該纖 維的長度對其平均直徑的比例。較佳者爲使用由具有高縱 橫比的各向異性粒子所組成的固體物質，該縱橫比係在5 至1〇，0〇〇之間，較佳者在1〇至1〇，0〇0之間 ，且更佳者在1〇0至10，000之間。 適當的層狀無機材料包括平均縱橫比爲5至 1 0，0 0 0的板。該板即具有約2 . 5毫微米或更小的 平均厚度，及1 0毫微米，較佳者約0 . 4毫微米至約 2 . 5毫微米之間，更佳者在約0 . 4毫微米至約2毫微 米之間的最大厚度。板的平均長度較佳者爲約2毫微米至 1，0 0 0毫微米。適當的層狀無機材料之例子爲葉矽酸 鹽，例如近晶狀黏土礦物質（s m e c 11 c c 1 a y m 1 n e r a 1 )，輕 石黏土礦物質和雲母，及合成雲母。適當的近晶狀黏土礦 物質之例子爲蒙脫土、囊脫石、貝得石、volkonskoite、水 輝石、富鎂蒙脫石、pyroysite、官石、sauconite、 magadnte、膨土、肯亞石（kenyaite )。較佳者爲選用蒙脫 土。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂----------線 mil (請先閱讀背面之注意事項再填寫本頁) -8- 1263579 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（6 ) 適當纖維狀無機材料中的個別纖維5至1 0，0 0 〇 的平均縱橫比◦該個別纖維的直徑即爲約1 0毫微米或更 小，且其最大直徑爲2 0毫微米，較佳者約〇 · 5毫微米 至約1 0毫微米之間，更佳者在約〇 · 5毫微米至約5毫 微米之間。該適當纖維狀無機材料中的個別纖維之平均長 度常爲約2，0 0 〇毫微米或較短者，其最大長度爲約 10，000毫微米，較佳者爲約20毫微米至200毫 微米，更佳者爲約4 0毫微米至1 0 0毫微米。適當纖維 狀無機材料的例子爲imogolite和氧化釩。 毫微塡料的用量可以自由選擇；該量決定於例如要得 到的經擠壓模製部件的合意性質及於如所選的聚縮合物， 該毫微-塡料的脫層程度及在該聚縮合物中的分散程度。 於本申請案中，’毫微塡料’要了解者爲商業上可得之經聚集 形式的塡料和經解聚集與脫層形式的塡料兩者，如在經擠 壓模製部件中所看到者。該毫微-塡料可不經預處理或改 質過或其可經預處理或改質過，例如用以促進脫層者◦於 完全分散和脫層的情況中，毫微-塡料的量較佳者爲相對 於聚縮合物的0 · 1 - 1 〇重量％。較佳者聚醯胺中的毫 微-塡料含量爲相對於聚醯胺的0 · 1 - 1 〇重量％，更 佳者0 · 2 — 7 · 5重量％。其最低量和最大量可以由諳 於此技者輕易地決定，因爲其含量低於最低量及高於最大 量的組成物係難以得到經擠壓模製部件之故。 本發明經擠壓模製部件可視情況包括添加劑，例如塡 料和強化材料，例如玻璃纖維和矽酸鹽，例如滑石，阻燃 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) - 9 - 1263579 A7Ver lag, and the references mentioned therein. For the nano-tank, any material known to those skilled in the art can be used. In particular, 'nano-drafts' are known to be solid materials composed of anisotropic particles having a high aspect ratio, such as layered or fibrous inorganic materials. The aspect ratio of the examples is understood in the present invention as the ratio of the largest dimension to the smallest dimension of the individual particles. More specifically, the aspect ratio of a panel is the ratio of the length of the panel to its average thickness, and the aspect ratio of a fiber is the ratio of the length of the fiber to its average diameter. Preferably, a solid material consisting of anisotropic particles having a high aspect ratio is used, the aspect ratio being between 5 and 1 〇, 0 ,, preferably between 1 〇 and 1 〇, 0 〇 0 Between, and better between 1 and 0 to 10,000. Suitable layered inorganic materials include plates having an average aspect ratio of 5 to 10,0 0 0. The plate has an average thickness of about 2.5 nm or less, and 10 nm, preferably from about 0.4 nm to about 2.5 nm, more preferably about 0.4. The maximum thickness between nanometers to about 2 nanometers. The average length of the sheet is preferably from about 2 nanometers to about 1,0 nanometers. Examples of suitable layered inorganic materials are sulphate salts, such as smectic clay minerals (s m e c 11 c c 1 a y m 1 n e r a 1 ), pumice clay minerals and mica, and synthetic mica. Examples of suitable smectic clay minerals are montmorillonite, nontronite, beidellite, volkonskoite, hectorite, magnesia-rich montmorillonite, pyroysite, official stone, sauconite, magadnte, bentonite, kanya stone ( Kenyaite). The preferred one is montmorillonite. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -------------------- Order---------- Line mil (please read the note on the back and fill out this page) -8- 1263579 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed 5, invention description (6) Individual fibers 5 to 1 in appropriate fibrous inorganic materials 0,0 0 The average aspect ratio of the crucible ◦ the diameter of the individual fibers is about 10 nm or less, and the maximum diameter thereof is 20 nm, preferably about 〇·5 nm to about 10 m. Between the micrometers, more preferably between about 5 nanometers and about 5 nanometers. The individual fibers of the suitable fibrous inorganic material typically have an average length of about 2,0 〇 nanometers or less, and have a maximum length of about 10,000 nanometers, preferably about 20 nanometers to 200 millimeters. Micrometers, more preferably from about 40 nanometers to about 100 nanometers. Examples of suitable fibrous inorganic materials are imagolite and vanadium oxide. The amount of nano-tanning material can be freely selected; the amount is determined, for example, by the desired properties of the extruded part to be obtained and, for example, the polycondensate selected, the degree of delamination of the nano-dye and The degree of dispersion in the polycondensate. In the present application, 'nano-batch' is understood to be both commercially available aggregated forms of dip and both deagglomerated and delaminated forms of dip, as in extruded parts. Seen. The nano-dye can be pre-treated or modified or it can be pre-treated or modified, for example to promote delamination in the case of complete dispersion and delamination, the amount of nano-draft It is preferably 0. 1 - 1 〇 by weight relative to the polycondensate. Preferably, the nano-twist content in the polyamide is 0. 1 - 1 〇 by weight relative to the polyamine, more preferably 0 · 2 - 7.5 % by weight. The minimum amount and the maximum amount can be easily determined by the skilled artisan, since it is difficult to obtain an extruded molded part because the composition is lower than the minimum amount and higher than the maximum amount. The extruded molded parts of the present invention may optionally include additives such as tanning materials and reinforcing materials such as glass fibers and silicates, such as talc, which are suitable for the Chinese National Standard (CNS) A4 specification (210 X 297 metric). PCT) -------- order --------- line (please read the note on the back and then fill out this page) - 9 - 1263579 A7

五、發明說明（7 ) 劑’發泡劑，安定劑，流動促進劑和顏料。 (請先閱讀背面之注意事項再填寫本頁) 本發明經擠壓模製部件可由一層或數層所組成；於後 述情況中，其他層可包括例如聚烯烴，如聚乙烯或聚乙烯 共聚物，如從乙烯和（甲基）丙烯酸所得的共聚物，或障 壁聚合物，如聚偏二氯乙烯或得自乙烯和乙烯醇的共聚物 〇 本發明也有關一種利用擠壓製造聚縮合物毫微複合物 料模製部件之方法，其特徵在於該模製部件係用一種組成 物擠壓成者，其中該組成物包括至少一聚縮合物其熔融可 加工性爲使得該聚縮合物本身不適合擠壓應用；和一種毫 微一塡料。 特別者，可以使用已知技術來製造本發明經擠壓模製 部件，例如擠壓、共擠壓、吹膜、型件擠壓、發泡擠壓、 吹模、深抽、延迓和紡絲。於膜的情況中，.可以實施擠壓 或共擠壓例如藉助冷卻輥技術或利用吹膜。 經濟部智慧財產局員工消費合作社印製 可以根據本發明製造本發明經擠壓模製部件所用得組 成物可用諳於此技者所知的多種方法得到，例如利用在毫 微一塡料存在中進行單體的聚合，如在E P — A 2 -6 0 5，0 0 5中所公開者，或經由將聚縮合物與毫微一 塡料熔融混合，如藉助於擠壓機者，例如使用根據u S -5 ，385 ，776 的方法（Allied Signal Inc.)。要得到 合意性質時，重要者爲毫微-塡料在聚縮合物中有良好的 分散和脫層。 本發明經擠壓模製部件可特別地以例如膜的形式用爲 $紙張中國國家標準（CNS)A4規格（210 X 297公釐） -10- 1263579 A7 ~~_ _B7 —---- 五、發明說明（8 ) 包裝膜，例如用以包裹食物，如乳酪和香腸者。 至此，本發明要參照諸實施例予以解說，但本發明不 受彼等所限制。 實A例I — V I I及比較例A和B :聚醯胺平膜_ 使用有下列性質的Gottfert擠壓機（616型）製造-系列平膜： 螺桿直徑30毫米，長度2〇xD，膜頭寬150毫 米，擠壓機溫度2 5 0 °C，冷卻輥溫度1 1 〇 °C ° ---------"4 (請先閱讀背面之注意事項再填寫本頁) 聚醯胺 Akulon® K123 :注模級聚醯胺 DSM N.V·，荷蘭）。 Akulon® F132E :膜級聚醯胺6 DSM N.V·，荷蘭）◦ 相對黏度2 . 8 相對黏度4 ·〇 訂 線 經濟部智慧財產局員工消費合作社印製 毫微-塡料V. INSTRUCTIONS (7) Agents 'Blowing agents, stabilizers, flow promoters and pigments. (Please read the note on the back and then fill out this page.) The extruded molded part of the present invention may be composed of one or several layers; in the latter case, other layers may include, for example, a polyolefin such as polyethylene or polyethylene copolymer. , for example, a copolymer obtained from ethylene and (meth)acrylic acid, or a barrier polymer such as polyvinylidene chloride or a copolymer derived from ethylene and vinyl alcohol. The present invention also relates to a method for producing a polycondensate by extrusion. A method of molding a part of a micro-composite material, characterized in that the molded part is extruded with a composition, wherein the composition comprises at least one polycondensate whose melt processability is such that the polycondensate itself is not suitable for extrusion Pressure application; and a nano-dip. In particular, the extrusion molding of the present invention can be carried out using known techniques, such as extrusion, co-extrusion, blown film, extrusion, foam extrusion, blow molding, deep drawing, laundering and spinning. wire. In the case of a film, extrusion or co-extrusion may be carried out, for example, by means of a chill roll technique or by using a blown film. Ministry of Economic Affairs Intellectual Property Office Employees Consumption Cooperative Printing The compositions used in the manufacture of the extruded molded parts of the present invention in accordance with the present invention can be obtained by a variety of methods known to those skilled in the art, for example, in the presence of a nano-draft. The polymerization of the monomers is carried out, as disclosed in EP-A 2 -6 0 5,0 0 5, or by melt mixing the polycondensate with the nano-powder, such as by means of an extruder, for example According to the method of u S-5, 385, 776 (Allied Signal Inc.). In order to obtain a desirable property, it is important that the nano-dye material has good dispersion and delamination in the polycondensate. The extruded molded part of the present invention can be used, for example, in the form of a film, as a paper China National Standard (CNS) A4 specification (210 X 297 mm) -10- 1263579 A7 ~~_ _B7 —---- , invention description (8) packaging film, for example, to wrap food, such as cheese and sausage. So far, the invention has been described with reference to the embodiments, but the invention is not limited thereto. Real Example I - VII and Comparative Examples A and B: Polyamide Flat Film _ Manufactured using a Gottfert extruder (Model 616) having the following properties - Series flat film: Screw diameter 30 mm, length 2 〇 x D, film head 150mm wide, extruder temperature 2 50 °C, chill roll temperature 1 1 〇 °C ° ---------"4 (Please read the note on the back and fill out this page) Amine Akulon® K123: injection molded grade polyamine DSM NV·, Netherlands). Akulon® F132E: Membrane Polyamide 6 DSM N.V·, Netherlands) 相对 Relative Viscosity 2.8 Relative Viscosity 4 · 〇 Order Line Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Nano-塡

Cloisite 20A (蒙脫土黏土，Southern Clay Products, USA )，包括6 0重量％的矽酸鹽和4 0重量％的有機物 質（季銨鹽）。表中所示量係相對於矽酸鹽含量。 聚醯胺毫微複合物料組成物係經由將該聚醯胺與含有 8 0重量％毫微-塡料（矽酸鹽）的聚醯胺毫微複合物料 母料（masterbatch )在擠壓機內熔融混合而製成。 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -11 - 1263579 A7 B7______ 五、發明說明（9 ) (請先閱讀背面之注意事項再填寫本頁) 其結果摘列於表1之中。彼等顯示出只使用有低黏度 的聚醯胺不可能製得一膜，而使用本發明組成物可以製得 良好的膜◦表1和下面諸表中的所有黏度係用聚醯胺在間 一甲酚中的1 %溶液在2 5 °C下測定者。 表1 :聚醯胺平膜 實 施 例 聚醯胺 毫微-塡料（ 重量 %) 加工參數 熔融加工性 Q(rpm) V(捲繞） (米/分） A K123 0 80 20 不能製成；熔融強度不夠 I K123 0.1 60 20 不能製成；熔融強度不夠 II K123 0.2 60 20 好膜 III K123 1 60 20 好膜 IV K123 2.5 60 20 好膜 V K123 5 60 20 好膜 VI K123 7.5 60 20 不一致的加工行爲；不良 膜 VII K123 10 60 30 不能製成；膜不能抽取 B F132E 0 60 20 良好的膜 經濟部智慧財產局員工消費合作社印製 實施例v I I I和比較例c與D : 管狀膜之製造 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -12- 1263579 A7 __________B7__ 五、發明說明（10 ) 使用有下列性質的Collin ( 1 3 0型）製造一系列管 狀膜： (請先閱讀背面之注咅P事項再填寫本頁) 螺桿直徑2 5毫米，長度2 0 X D，標準通用型螺桿 ;冷卻輥尺寸 1 2 6 X 6 0 0毫米；橡膠輕尺寸 72 X 6 0 0毫米；最大開放線圈徑長2 5毫米。溫度2 5 0 °C ;吹滿比 3。 聚醯胺 A k u 1 ο η ® K 1 2 3 :注模級聚醯胺6，相對黏度2 · 8 ( DSM N.V·，荷蘭）。 A k u 1 ο n ® F 1 3 6 E :膜級聚醯胺6，相對黏度4 · 3 ( DSM N.V·，荷蘭）。 毫微一塡料Cloisite 20A (montmorillonite clay, Southern Clay Products, USA) comprises 60% by weight of citrate and 40% by weight of organic matter (quaternary ammonium salt). The amounts shown in the table are relative to the citrate content. The polyamidamine nanocomposite composition is obtained by passing the polyamine with a polybamine nanocomposite masterbatch containing 80% by weight of nano-nake (cartrate) in an extruder. Made by melt mixing. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -11 - 1263579 A7 B7______ V. Invention description (9 ) (Please read the note on the back and fill out this page) In Table 1. They have shown that it is not possible to obtain a film using only low viscosity polyamines, but a good film can be obtained using the composition of the invention. Table 1 and all the viscosity lines in the following tables are made with polyamine. The 1% solution in cresol was measured at 25 °C. Table 1: Polyimine flat film examples Polyamide niobium-niobium (% by weight) Processing parameters Melt processability Q (rpm) V (winding) (m/min) A K123 0 80 20 Can not be made; Insufficient melt strength I K123 0.1 60 20 Can not be made; insufficient melt strength II K123 0.2 60 20 Good film III K123 1 60 20 Good film IV K123 2.5 60 20 Good film V K123 5 60 20 Good film VI K123 7.5 60 20 Inconsistent Processing behavior; poor film VII K123 10 60 30 can not be made; film can not be extracted B F132E 0 60 20 good film economic department intellectual property bureau employee consumption cooperative printing example v III and comparative examples c and D : manufacturing of tubular film This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) -12- 1263579 A7 __________B7__ V. INSTRUCTIONS (10) A series of tubular membranes are manufactured using Collin (type 130) with the following properties: (Please read the back note 咅P and then fill out this page) Screw diameter 2 5 mm, length 2 0 XD, standard universal screw; chill roll size 1 2 6 X 650 mm; rubber light size 72 X 6 0 0 mm; maximum open coil length 2 5 mm. Temperature 2 5 0 °C; blow ratio 3 . Polyamine A k u 1 ο η ® K 1 2 3 : Injection molded grade polyamide 6, relative viscosity 2 · 8 (DSM N.V., Netherlands). A k u 1 ο n ® F 1 3 6 E : Membrane-grade polyamide 6, relative viscosity 4 · 3 (DSM N.V., Netherlands). Minor one

Cloisite 20A (蒙脫土黏土，Southern Clay Products， USA )，包括6 0重量％的矽酸鹽和4 0重量％的有機物 質（季銨鹽）。表中所示量係相對於矽酸鹽含量。 經濟部智慧財產局員工消費合作社印製 聚醯胺毫微複合物料組成物係經由將該聚醯胺與含有 8 0重量％毫微-塡料（矽酸鹽）的聚醯胺毫微複合物料 母料組成物在擠壓機內熔融混合而製成。 其結果摘列於表2之中。彼等顯示出將少量的毫微-塡料加到有低黏度的聚醯胺可以導致熔融加工性的增加因 而可以得到良好的管狀膜。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -13- 1263579 A7 -- ---B7 五、發明說明（11 ) 表2 :聚醯胺管狀膜 實施例 聚醯胺 毫微-塡料（重量％) 膜 一 C K123 0 不能製成；熔融強度不夠 VIII K123 5 好膜；隨著吹滿比的增加 G-4-4.5)膜的透明性遞 增 D F136E 0 好膜 (請先閱讀背面之注意事項再填寫本頁) 實施例I X - X I和比較例E :聚醯J安板 製造 使用有下列性質的Schabenthan製造一系列的板： 頭寬 1 5 0毫米；平滑進料段；擠壓溫度2 5 Ο ΐ： ;冷卻f昆溫度 4 0 °C ;模頭寬 1 · 9毫米；輥之間的 間隙寬度 1毫米；速度5 0 r p m。 聚醯胺 經濟部智慧財產局員工消費合作社印製Cloisite 20A (montmorillonite clay, Southern Clay Products, USA) comprises 60% by weight of citrate and 40% by weight of organic matter (quaternary ammonium salt). The amounts shown in the table are relative to the citrate content. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed Polyamine Nanocomposite Material Composition via Polyamide and Polyamido Nanocomposite Material Containing 80% by Weight of Nano-Tanning (Citrate) The masterbatch composition is prepared by melt mixing in an extruder. The results are summarized in Table 2. They have shown that the addition of a small amount of nano-twist to a low viscosity polyamine can result in an increase in melt processability, resulting in a good tubular film. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -13- 1263579 A7 -- --- B7 V. Description of invention (11 ) Table 2: Polyamide film example Polyamide Nano-twist (wt%) Membrane-C K123 0 can not be made; the melt strength is not enough VIII K123 5 good film; as the blow ratio increases G-4-4.5) the transparency of the film increases D F136E 0 good film (Please read the notes on the back and then fill out this page.) Example IX - XI and Comparative Example E: Poly-J-plate fabrication A series of plates were made using Schabenthan having the following properties: head width 150 mm; smoothing Section; extrusion temperature 2 5 Ο ΐ: ; cooling f Kun temperature 40 ° C; die width 1 · 9 mm; gap width between rolls 1 mm; speed 50 rpm. Polyamide, Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

Akulon® F135C :擠壓級聚醯胺6，相對黏度4 · 1 ( DSM N.V·，荷蘭）。 毫微-塡料Akulon® F135C: Extruded grade polyamide 6, with a relative viscosity of 4 · 1 (DSM N.V., Netherlands). Nano-data

Cloisite 20A (蒙脫土黏土，Southern Clay Products, USA) ，包括6 0重量％的矽酸鹽和4 0重量％的有機物質（季 銨鹽）。表中所示量係相對於矽酸鹽含量。 聚醯胺毫微複合物料組成物係經由將該聚醯胺與含有 ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ' -14- 1263579 A7 五、發明說明（12 )Cloisite 20A (montmorillonite clay, Southern Clay Products, USA) comprises 60% by weight of citrate and 40% by weight of organic matter (quaternary ammonium salt). The amounts shown in the table are relative to the citrate content. The polyamidamine nanocomposite material composition is based on the polyamine and the paper containing the Chinese National Standard (CNS) A4 specification (210 X 297 mm) '-14- 1263579 A7 5. Invention Description (12)

Akul〇n® K 1 2 3 + 5重量％毫微—塡料的母料在擠壓機 內熔融混合而製成。 其結果摘列於表3之中。彼等顯示出將少量的毫微一 塡料加到聚醯胺中可以導致熔融加工性的增加因而可以防 止板的沉降（sagging )。令人訝異者，也可以得到更好的 光澤和更大的透明度。擠壓過程中的板沉降是一種熟知的 發生於注模模頭與第一輥之間的現象。沉降可經由增加熔 融加工性予以防止。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表3 :聚醯胺管狀膜 實施例 聚醯胺 毫微-塡料 (重量％) 板 E F135C 0 不觀察到板的沉降 IX F135C 0.25 較少的沉降現象 X F135C 0.5 沒有沉降 XI F135C 1 沒有沉降 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） - 15-A masterbatch of Akul〇n® K 1 2 3 + 5 wt% nano-twist is melt-mixed in an extruder. The results are summarized in Table 3. They have shown that the addition of a small amount of nano-twist to polyamine can result in an increase in melt processability and thus prevent sagging of the sheet. Surprisingly, you can get better gloss and greater transparency. Plate settling during extrusion is a well-known phenomenon that occurs between the injection molding die and the first roll. Settling can be prevented by increasing the meltability. (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 3: Polyamide Tubular Film Example Polyamide Nano-塡 (wt%) Plate E F135C 0 No Sedimentation of the plate was observed IX F135C 0.25 Less sedimentation X F135C 0.5 No sedimentation XI F135C 1 No sedimentation Paper scale applicable to China National Standard (CNS) A4 specification (210 x 297 mm) - 15-

Claims (1)

1263579 A8 B8 C8 ‘ ‘ D8 …^ ---—-r----J-------- 穴、申請專利範圍 ^ 1Z 14 附件2八·· 桌8 9 1 1 7 5 3 1號專利申請案 中文申請專利範圍替換本 民國9 3年1 2月14日修正 1 · 一種經擠壓模製部件，其包含一種具有相對黏度 最高爲2 · 8之聚醯胺（該相對黏度爲用該聚醯胺在間-甲酚中的1 %溶液於2 5 °C下所測得）和一種毫微塡料（ 其量相對於該聚醯爲〇 . 2至5重量％ )，其中該毫微塡 料爲具有縱橫比爲5至1 0，0 〇 〇之間的由各向異性粒 子所組成之固體物質。 - 2 .如申請專利範圍第1項之經擠壓模製部件，其中 該毫微塡料爲纖維狀無機材料。 3 .如申請專利範圍第1項之經擠壓模製部件，其中 該毫微塡料爲由具有2毫微米至1 〇 〇 〇毫微平均長度之 板所構成之層狀無機材料。 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 4 ·如申請專利範圍第3項之經擠壓模製部件，.其中 該毫微塡料爲近晶狀黏土礦物質。 5 .如申請專利範圍第4項之經擠壓模部件，其中該 近晶狀黏土礦物質爲蒙脫土。 6 .如申請專利範圍第1 - 5項中任一項之經擠壓模 製部件，其中該模製部件爲膜，薄壁物體，厚壁物體，發 泡體，或纖維。 7 · —種利用擠壓製造聚醯胺毫微複合物料模製部件 ( 21〇Χ 297(ί"ϊ ^ ' ABCD 1263579 六、申請專利範圍 之方法，其特徵在於該模製部件係使用一組成物壓製成， 該組成物包含一種具有相對黏度最高爲2 · 8之聚醯胺（ δ次相對黏度爲用5亥聚釀胺在間-甲酣中的1 %溶液於2 5 °C下所測得）和一種毫微塡料（其量相對於該聚醯爲 〇·2至5重量％)，其中該毫微塡料爲具有縱橫比爲5 至1 0，0 0 0之間的由各向異性粒子所組成之固體物質 〇 8 ·如申請專利範圍第7項之方法，其中該毫微塡料 爲近晶狀黏土礦物質。 9 ·如申請專利範圍第8項之方法，其中該近晶狀黏 土礦物質爲蒙脫土。 1 〇 ·如申請專利範圍第7至9項中任一項之方法， 其中所製得之經擠壓模製部件爲一薄膜。 ----------——费一, (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本纸張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐）1263579 A8 B8 C8 ' ' D8 ...^ -----r----J-------- Hole, patent application scope ^ 1Z 14 Attachment 2 VIII· Table 8 9 1 1 7 5 3 1 Patent Application for Chinese Patent Application Replacement of the Republic of China 1983 1 February 14 Revision 1 · An extruded molded part comprising a polyamidamide having a relative viscosity of up to 2 · 8 (the relative viscosity is Using a 1% solution of the polyamine in m-cresol at 25 ° C) and a nano-powder (the amount of which is 〇. 2 to 5% by weight relative to the polyfluorene), wherein The nano-powder is a solid material composed of anisotropic particles having an aspect ratio of 5 to 10,0 Å. - 2. The extruded molded part of claim 1, wherein the nano-material is a fibrous inorganic material. 3. The extruded molded part of claim 1, wherein the nano-powder is a layered inorganic material composed of a plate having a nano-average length of from 2 nm to 1 〇 。. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives (please read the notes on the back and fill out this page). 4 · If you are applying the extruded part of the third paragraph of the patent, the nano-material is smectic. Clay minerals. 5. The extruded mold part of claim 4, wherein the smectic clay mineral is montmorillonite. 6. The extruded molded part of any one of claims 1 to 5, wherein the molded part is a film, a thin-walled object, a thick-walled object, a foamed body, or a fiber. 7 - a method for producing a polyamide-based nanocomposite molded part by extrusion (21 〇Χ 297 (ί" ϊ ^ ' ABCD 1263579 s, a method of patent application, characterized in that the molded part is composed of a composition Made of barium, the composition comprises a polyamidamide having a relative viscosity of up to 2 · 8 (the relative viscosity of δ is a 1 % solution in 5 - mercaptoamine at 25 ° C Measured) and a nano-dye (the amount is 〇·2 to 5% by weight relative to the polyfluorene), wherein the nano-twist is an aspect having an aspect ratio of 5 to 10,0 0 A solid material consisting of anisotropic particles 〇8. The method of claim 7, wherein the nano-tanning material is a smectic clay mineral. 9 - The method of claim 8 wherein the near The crystalline clay mineral is a montmorillonite. The method of any one of claims 7 to 9, wherein the extruded molded part is a film. ----——Fei Yi, (Please read the notes on the back and fill out this page) This paper printed cooperatives fee scale applicable Chinese National Standard (CNS) A4 size (210X29? Mm)